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1.
The partitioning of samarium and thulium between garnets and melts in the systems Mg3Al2-Si3O12-H2O and Ca3Al2Si3O12-H2O has been studied as a function of REE concentration in the garnets at 30 kbar pressure. Synthesis experiments of variable time under constant P, T conditions indicate that garnet initially crystallizes rapidly to produce apparent values of D Sm (D Sm=concentration of Sm in garnet/concentration of Sm in liquid) which are too large in the case of pyrope and too small in the case of grossular. As the experiment proceeds, Sm diffuses out of or into the garnet and the equilibrium value of D Sm is approached. Approximate values of diffusion coefficients for Sm in pyrope garnet obtained by this method are 6 × 10–13 cm2 s–1 at 1,300 ° C and 2 × 10–12 cm2 s–1 at 1,500 ° C, and for grossular, 8.3 × 10–12 cm2 s–1 at 1,200 ° C and 4.6 × 10–11 cm2 s–1 at 1,300 ° C. The equilibrium values of D Sm have been reversed by experiments with Sm-free pyrope and Sm-bearing glass, and with Sm-bearing grossular and Sm-free glass.Between 12 ppm and 1,000 ppm Sm in pyrope at 1,300 ° C and between 80 ppm and >2 wt.% Tm in pyrope at 1,500 ° C, partition coefficients are constant and independent of REE concentration. Above 100 ppm of Sm in garnet at 1,500 ° C, partition coefficients are independent of Sm concentration. At lower concentrations, however, D Sm is dependent upon the Sm content of the garnet. The two regions may be interpreted in terms of charge-balanced substitution of Sm3Al5O12 in the garnet at high Sm concentrations and defect equilibria involving cation vacancies at low concentrations. At very low REE concentrations (< 1 ppm Tm in grossular at 1,300 ° C) DREE garnet/liquid again becomes constant with an apparent Henry's Law value greater than that at high concentrations. This may be interpreted in terms of a large abundance of cation vacancies relative to the number of REE ions.The importance of defects in the low concentration region has been confirmed by adding other REE (at 80 ppm level) to the system Mg3Al2Si3O12-H2O at low Sm concentrations. These change D Sm in the defect region, demonstrating their role in the production of vacancies.Experiments on a natural pyropic garnet indicate that defect equilibria are of importance to REE partitioning within the concentration ranges found in nature.  相似文献   

2.
A suite of 11 gem-quality, optically completely clear garnet crystals with a broad variety of compositions in the space of the end members pyrope–almandine–spessartine–grossular–andradite–goldmanite were analyzed for trace amounts of “water” by nuclear reaction analysis, NRA, based on the reaction 1H(15N, αγ)12C, and by single-crystal absorption spectroscopy in the νOH vibrational range using microscope-FTIR-spectroscopic methods. The aim was to establish a calibration of the highly sensitive IR method with high areal resolution for “water” determination in garnets, by studying garnets of a wide compositional range, and to check for compositional dependencies of the integral molar absorptivities of the “water” component, ?int[1molH2O?1cm?2], in the nominally “water”-free garnets. The results of NRA show a broad variation of water contents in the range (14 ± 3) to (950 ± 80) wt ppmH2O, the values being low and very high for the garnet solid solutions (PyrAlm)SS and close-to-end-member GrossSS, respectively. There were no indications of inhomogeneities in the OH distribution, except possibly for one of the garnets (grossular, variety hessonite, from Tanzania). The quantitative evaluation of the complex νOH spectra, which showed similar shape only for members of the (PyrAlm)SS, yielded integral absorption coefficients, αint (cm?2), which allowed the calculation of integral molar absorptivities, ?int, using the “water” values of NRA. The ?int values obtained varied in a wide range but with no obvious correlation with the composition of the garnet except for the extremely high values, in the 104 range, of the two specimen with compositions close to end-member grossular. In all other garnets, ?int was in the 103 range with an average of ?int=3630±1580[1molH2O?1cm?2]. Therefore, this value is proposed for the use in routine “water” determinations of compositionally different garnets by the micro-IR method, except for garnets near to end-member grossular.  相似文献   

3.
 The hydrothermal reaction between grossular and 1 molar manganese chloride solution was studied at 2 kbar and 600 °C at various bulk Ca/(Ca+Mn) compositions: Ca3Al2Si3O12+3Mn2+(aq) ⇔ Mn3Al2Si3O12+3Ca2+(aq) The reaction products are garnets of the spessartine-grossular solid-solution series which discontinuously armour the dissolving grossular grains. The first garnet to crystallize is spessartine rich (X gt Mn≥0.95), reflecting the high Mn content of the solution, but as the reaction proceeds more calcium-rich garnets progressively overgrow the initial products. The armouring product layer is detached from the dissolving grossular, which allows the progressive overgrowth to occur on both its external and internal surfaces and results in the development of a two directional Ca/(Ca+Mn) zoning pattern in the product grains. The compositional changes in the run products are consistent with attainment of heterogeneous equilibrium between the external rims of the spessartine-grossular garnets and the bulk solutions in runs of duration ≥24 hours. Plots of ln KD versus X gt Ca maxima show linear variations that are not consistent with the ideal mixing that has been proposed for spessartine-grossular garnets at temperatures of 900 to 1200 °C. The data rather fit a regular solution model with the parameters ΔG° (600 °C, 2 kbar)=−8.0±0.8 kJ/mol and w gt CaMn=2.6±2.0 kJ/mol. Existing solubility measurements and thermodynamic data from other Ca and Mn silicates support the calculated data. Grossular activities calculated using the w gt CaMn parameter indicate that even in manganese-rich metapelites pressure estimates calculated using the garnet-plagioclase-Al2SiO5-quartz barometer will not be increased by more than 0.2 kbar. Received: 18 January 1995/Accepted: 4 June 1996  相似文献   

4.
Activity-composition relationships for pyrope-grossular garnet   总被引：1，自引：0，他引：1  
Activity coefficients () for grossular in pyrope-grossular garnet have been determined experimentally using the divariant assemblage garnet-anorthite-sillimanite (kyanite)-quartz. Values of for garnets with 10–12 mole % grossular have been obtained at 1000 °, 1100 °, 1200 ° and 1300 ° C at pressures between 15 and 21 Kb. The data are consistent with a symmetrical regular solid model for grossular-pyrope solid solutions. The interaction parameter (W) increases linearly with decreasing temperature and is given by W = 7460-4.3 T cals (T in °K). A solvus in the pyrope-grossular solid solution is predicted with a temperature of critical mixing of 629°C±90 ° C.  相似文献   

5.
The compression of synthetic pyrope Mg3Al2 (SiO4)3, almandine Fe3Al2(SiO4)3, spessartine Mn3Al2 (SiO4)3 grossular Ca3Al2(SiO4)3 and andradite Ca3Fe2 (SiO4)3 was studied by loading the crystals together in a diamond anvil cell. The unit-cell parameters were determined as a function of pressure by X-ray diffraction up to 15 GPa using neon as a pressure transmitting medium. The unit-cell parameters of pyrope and almandine were measured up to 33 and 21 GPa, respectively, using helium as a pressure medium. The bulk moduli, K T 0, and their first pressure derivatives, K T 0 ′, were simultaneously determined for all five garnets by fitting the volume data to a third order Birch-Murnaghan equation of state. Both parameters can be further constrained through a comparison of volume compressions between pairs of garnets, giving for K T 0 and K T 0 ′ 171(2) GPa and 4.4(2) for pyrope, 185(3) GPa and 4.2(3) for almandine, 189(1) GPa and 4.2 for spessartine, 175(1) GPa and 4.4 for grossular and 157(1) GPa and 5.1 for andradite, where the K T 0 ′ are fixed in the case of spessartine, grossular and andradite. Direct comparisons of the unit-cell volumes determined at high pressures between pairs of garnets reveal anomalous compression behavior for Mg2+ in the 8-fold coordinated triangular dodecahedron in pyrope. This agrees with previous studies concerning the compression behaviors of Mg2+ in 6-fold coordinated polyhedra at high pressures. The results show that simple bulk modulus–volume systematics are not obeyed by garnets. Received: 29 July 1998 / Revised, accepted: 7 April 1999  相似文献   

6.
Garnet in silicic liquids and its possible use as a P-T indicator   总被引：1，自引：0，他引：1  
Melting experiments on a model pelitic composition yield low-spessartine garnet as an important residual phase at pressures above 7 kb. The K D values for distribution of iron and magnesium between coexisting garnet and liquid in the pelitic composition are mainly sensitive to temperature, but also have a small pressure dependence. At temperatures above 950 ° C garnet has a higher value than coexisting liquid, but below 950 ° C the garnet value is lower than that of the coexisting liquid. Thus at temperatures below 950 ° C silicic magmas may fractionate garnet and produce more magnesian derivative liquids.Reconnaissance experiments with added MnO content in the model pelite demonstrate that spessartine-rich garnets are stable in silicic liquids to pressures as low as 3 kb. The MnO and CaO contents of the experimentally crystallized garnets show an antipathetic relation. Also, the grossular content of near-liquidus garnets crystallizing from a range of compositions increases with increasing pressure. The spessartine and grossular contents of most natural garnets in eastern Australian granitic rocks suggest that these garnets formed at pressures greater than 5 kb. Increased spessartine content allows crystallization of garnet in equilibrium with a silicic magma well within the pressure limit of stability of cordierite, provided the garnet contains 10 mol.% spessartine. Thus the depth range over which garnet and cordierite may coexist in a silicic melt is broadened, subject to the availability of MnO. The effect of increased Mn content on the low-pressure stability limit of garnet may also explain the lack of resorption of some garnets in granitic magmas, as these magmas rise to shallower levels. These euhedral garnets characteristically show zoning from an Mn-poor core (typically <4 % MnO) to an Mn-richer rim (typically >4 % MnO) and may reflect continued growth of the garnet in a low pressure regime, stabilized by Mn concentrated in the residual liquid fractions of the crystallizing magma.  相似文献   

7.
Three garnet-biotite pairs and eleven garnet-cordierite-biotite triplets from the Steinach aureole (Oberpfalz, North-East Bavaria) were analyzed using an electron probe microanalyzer.The regional metamorphic muscovite-biotite schists contain garnets strongly zoned with Mn-Ca-rich centers and Fe-rich edges, the average composition being almandine 67 — spessartine 4 — pyrope 4 — grossular (+andradite) 25.The first contact garnet that is formed in mica schists of the outermost part of the aureole is small, virtually unzoned, and has an average composition of almandine 52 — spessartine 37 — pyrope 8 — grossular (+andradite) 3. With increasing metamorphic grade, there is a consistent trend to form garnets richer in Fe ending up with a composition almandine 84.5 — spessartine 5.5 — pyrope 7.5 — grossular (+andradite) 2.5. This trend is accompanied by a general increase in grain size and modal amount of garnet. Associated cordierites and biotites also become richer in Fe with increasing grade. While the garnets in the highest grade sillimanite hornfelses are poorly zoned, the transitional andalusite-sillimanite hornfelses contain garnets with distinct but variable zonation profiles.These facts can possibly be explained by the time-temperature relationships in the thermal aureole. In a phase diagram such as the Al-Fe-Mg-Mn tetrahedron, the limiting mineral compositions of a four-phase volume or a three-phase triangle are fixed by T and P (the latter remaining effectively constant within a thermal aureole). Thus, in garnet-cordierite-biotite assemblages, garnet zonation should be controlled by temperature variation rather than by a non-equilibrium depletion process. Taking into account the experimental data of Dahl (1968), a zoned garnet from a transitional andalusite-sillimanite hornfels would reflect a temperature increase of about 40° C during its growth. A hypothetical P-X diagram is proposed to show semi-quantitatively the compositional variation of garnet-cordierite pairs with varying pressures (T constant).  相似文献   

8.
Garnets in epidote-bearing gneisses and mica schists from the western Hohe Tauern, Austria, have been analyzed by optical, x-ray powder diffraction, wet chemical and electron microprobe methods.The garnets frequently show zonal structure and their core compositions are in the range 45–52% grossular, 31–44% almandine, 3–13% spessartine, 0–7% andradite and 0–2% pyrop. The refractive indices n=1.780–1.786 and the lattice parameter a=11.68–11.73 Å likewise are intermediate between almandine and grossular. It is suggested that there is complete solid solution between almandine and grossular, at least under the conditions of greenschist to low-temperature amphibolite facies of regional metamorphism of the Tauern area.

Prof. Dr. F. Karl starb am 15. 8.1972.

Dank. Die Mikrosonde wurde von der Stiftung Volkswagenwerk bereitgestellt, und die Probenahme wurde von der Deutschen Forschungsgemeinschaft unterstützt. Wir danken Herrn Dr. P. K. Hörmann (Kiel) für die naßchemische Granatanalyse und Herrn Dr. K. Abraham (Bochum) für die Bereitstellung seines Korrekturprogrammes für Mikrosondenanalysen.  相似文献   

9.
Summary Sonoraite, FeTeO3(OH)·H2O, is monoclinic,P 21/c, witha=10.984(2),b=10.268(2),c=7.917(2) Å, =108.49(2)°. For 8 formula units per cell the calculated density is 4.179(2) g/cm3; the observed value is 3.95(1) g/cm3. The Supper-Pace automated diffractometer was used to collect 1884 independent reflections which were corrected for absorption. The structure was determined by an automated symbolic addition procedure. It was refined to a residualR of 6.2% using anisotropic temperature factors for the cations and isotropic temperature factors for the oxygen atoms. Chains of octahedra about Fe extend along [101]; edge-sharing pairs of these octahedra are joined by corner sharing. The Fe–Fe distances across the shared edges are 3.05 and 3.20 Å, short enough to suggest magnetic interactions. All but one H2O are involved in the chains. The Te4+ ions have a pseudotetrahedral coordination, with three oxygen ions forming one face of the tetrahedron and the lone electron pair of Te occupying the fourth corner. The O–Te–O average bond angle is 95°. The Fe chains are tied together by Te–O bonds in all three dimensions.
Die Kristallstruktur von Sonorait, Fe3+Te4+O3(OH).H2O
Zusammenfassung Sonorait, FeTeO3(OH)·H2O, ist monoklin, P 21/c, mit den folgenden Zelldimensionen:a=10,984(2),b=10,268(2),c=7,917(2) Å, =108,49(2)°. Mit 8 Formel-Einheiten errechnet man eine Dichte von 4,179(2) g/cm3; die gemessene Dichte beträgt 3,95(1) g/cm3. Das Supper-Pace automatische Diffraktometer wurde zur Sammlung von 1884 unabhängigen Reflexen benutzt, welche für Absorption korrigiert wurden. Die Struktur wurde mit Hilfe eines vollständig automatischen Programms für symbolische Addition bestimmt. Mit anisotropen Temperaturfaktoren für die Kationen und mit isotropen Temperaturfaktoren für die Sauerstoff-Atome wurde ein Residuum von 6,2% erreicht. Ketten von Eisen-Oktaedern erstrecken sich entlang [101]; Oktaeder-Paare mit gemeinsamen Kanten sind über Eckenverknüpfung verbunden. Die Fe–Fe-Abstände über die gemeinsamen Kanten betragen 3,05 und 3,20 Å, kurz genug, um zu magnetischer Wechselwirkung führen zu können. Nur ein H2O-Molekül ist nicht Teil einer Kette. Die Te4+-Ionen befinden sich in pseudotetraedrischer Koordination; drei Sauerstoff-Ionen bilden eine Fläche des Tetraeders, die vierte Ecke wird durch das einsame Elektronenpaar von Te besetzt. Der Mittelwert des O–Te–O-Bindungswinkels beträgt 95° Die Fe-Ketten werden durch Te–O-Bindungen dreidimensional verbunden.

With 3 Figures  相似文献   

10.
Raman and infrared spectroscopic data at ambient and high pressures were used to compute the lattice contribution to the heat capacities and entropies of six endmember garnets: pyrope, almandine, spessartine, grossular, andradite and uvarovite. Electronic, configurational and magnetic contributions are obtained from comparing available calorimetric data to the computed lattice contributions. For garnets with entropy in excess of the computed lattice contribution, the overwhelming majority is found in the subambient temperature regime. At room temperature, the non-lattice entropy is approximately 11.5 J/mol-K for pyrope, 49 J/mol-K for almandine, and 19 J/mol-K for andradite. The non-lattice entropy for pyrope and some for almandine cannot be accounted for by magnetic or electronic contributions and is likely to be configurational in nature. Estimates of low temperature non-lattice entropies for both spessartine and uvarovite are made in absence of calorimetric measurements and are based on low temperature calorimetry of other minerals containing the Mn2+ and Cr3+ cations as well as on solid solution garnets containing these cations. The estimate for uvarovite non-lattice entropy is approximately 18 J/mol-K, while for spessartine, approximately 45 J/mol-K. Neither of these cations is expected to provide electronic contributions to the entropy. For both iron-bearing garnets, a small electronic or magnetic entropy contribution continues above ambient temperatures. High pressure data on pyrope, grossular and andradite permit calculation of the thermodynamic parameters at high pressures, which are important for computation of processes in the Earth’s mantle. Thermal expansion coefficients of these materials were found to be 1.6, 1.5, 1.6×10−5 K−1 at 298 K, respectively, using a Maxwell relation. These closely match the literature values at ambient conditions.  相似文献   

11.
Summary Vivianite from Catavi Mine, Llallagua, Bolivia, has a near ideal composition with traces of Mg, Zn and Mn. Total rare-earth elements are < 1,gmg/g. Mössbauer spectroscopy shows FeIII/(FeII + FeIII) is approximately 0.04.a = 10.030Å,b = 13.434Å,c = 4.714Å, = 102.73dg. The middle-infrared powder spectrum shows H2O-related bands at 3490, 3290, 3130 cm–1 (stretch), 1618 cm–1 (bend), 825 cm–1 (rock), and at 665 cm–1 a possible M-OH2 twist. P04 bands occur at 1045-940 cm–1 (stretch) and 570-450 cm–1 (bend). Corresponding laser Raman microprobe bands occur at 1051 (ms), 986 (m), 948 (vs), 867 (mw), 828 (w), 568, 532, 453 (m), 442 (mw). Weak Raman bands at about 342, 303, 270 (w), 235 (ms), 227 (sh, ms), 196 (ms), 187 (sh, m), 162 (mw), and 126 (m) may arise from lattice vibrations. Differential thermal responses include a major endotherm from 115–235°C with a shoulder at 170°C and a maximum at 210°C resulting from loss of structural water combined with oxidation of Fe2+, and two small exotherms with maxima at 605 and 780°C related to structural transformations.
Charakterisierung des Vivianits von Catavi, Llallagua, Bolivien
Zusammenfassung Vivianit von der Catavi Mine, Llallagua, Bolivien zeigt annähernd ideale Zusammensetzung mit Spuren von Mg, Zn und Mn. Der gesamte Gehalt an seltenen EvolElementen ist < 1 ppm. Die Mössbauer Spektroskopie liefert ein Fe3+/(Fe2+ + Fe3+) Verhältnis von ungefähr 0.04.a = 10.030,b = 13.434,c = 4.714 Å, = 102.73°. Das Infrarot-Pulverspektrum zeigt dem H20 zuzuordnende Banden bei 3490, 3290, 3130 cm–1 (Streckschwingungen), 1618 cm–1 (Deformationsschwingung), 825 cm–1 (Schaukelschwingung) und eine mögliche M-OH2 Torsionsschwingung bei 665 cm–1. PO4 Banden liegen bei 1045-940 cm–1 (Streckschwingung) und 570-450 cm–1 (Deformations-schwingung). Entsprechende Banden der Laser Raman Mikrosonde liegen bei 1051 (mst), 986 (m), 948 (sst) 867 (mschw), 828 (schw), 568, 532, 453 (m), 442 (mschw). Raman Banden bei etwa 342, 303, 270 (schw), 235 (mst), 227 (Schulter, mst), 196 (mst), 187 (Schulter, m), 162 (mschw) und 126 (m) können auf Gitterschwingungen zurückgeführt werden. Differential-thermoanalytische Untersuchungen zeigen einen endothermen Bereich von 115–235°C mit einer Schulter bei 170 und einem Maximum bei 210°C, was auf den Verlust von strukturellem Wasser, das an eine Oxidation des Fe2+ gebunden ist, zurückzuführen ist; zwei auf strukturelle Transformationen zurückzuführende exotherme Maxima liegen bei 605 und 780°C.

With 4 Figures  相似文献   

12.
High-pressure synthesis of a new SrSi2O5 phase was performed at 16 GPa and 900°C by using a Kawai-type multianvil apparatus. The powder X-ray diffraction pattern of the compound was analyzed by Rietveld refinement based on the structure of a high-pressure polymorph of BaGe2O5, BaGe2O5 III. The structure is orthorhombic with space group Cmca and cell parameters of a = 5.2389(1) Å, b = 9.2803(2) Å, c = 13.4406(1) Å, V=653.46(2) Å 3 (Z=8, calc=4.549 g/cm3). The structure consists of layers containing SiO6 octahedra and SiO4 tetrahedra. In a unit layer, oxygen and strontium atoms are arranged in an approximation to hexagonal close-packing. The strontium atom is accommodated in a 12-coordinated site. Each SiO6 octahedron shares four corners with SiO4 tetrahedra and the other two corners with another SiO6 octahedra. The SiO6 octahedra are linked to each other to form SiO6 chains along the a-axis. This is the first known example of a silicate with a BaGe2O5 III-type structure.  相似文献   

13.
 The UV edge in the electronic absorption spectra of minerals, in many cases influencing their colour, is generally interpreted as the low-energy wing of very strong UV bands caused by ligand–metal charge transfer (CT) transitions (e.g. Burns 1993). However, Mie scattering theory shows that the presence of randomly distributed submicroscopic inclusions with narrow size distribution and a refractive index n i in a matrix with different refractive index n m may give rise to a λ-dependent, band-like scattering (e.g. Kortüm 1969). Such scattering bands have so far not been considered as contributing to the UV edge. Single-crystal electronic absorption spectra of eight natural almandine-rich garnets (Alm60–Alm88), two synthetic almandine samples (Alm100), all of different colours, and synthetic spessartine were studied by means of a Zeiss microscope-spectrometer in the range 40 000–20 000 cm−1. Special techniques of spectral measurements with crossed analyzer and polarizer, which enable the registration of the scattering effect directly, were used as well. Four of the above garnets were also investigated using transmission electron microscopy. Different types of inclusions, from 10 to several 100 nm in size, were observed in the garnet matrices. They are abundant in cores of synthetic garnets, but very rare in most natural almandines studied. Electronic absorption spectra of the natural almandine garnets show largely varying UV edge position and, hence, intensity at a given wavenumber which correlates with the intensities of spin-forbidden dd bands of Fe3+ ions at 27 000 and 28 000 cm−1, superimposed on the long energy slope of the UV absorption. There are also positive correlations between Ti4+ and Fe3+ content, the latter recalculated on the basis of garnet stoichiometry, and UV edge intensity. Thus, the presence of Ti4+ and Fe3+ ions in octahedra, even in very low concentrations (0.0n at. pfu), leads to CT phenomena, that probably involve Fe2+ ions in edge-shared dodecahedral position and intensifies ligand- to-metal CT. The different colours of natural almandine garnets with similar Fe2+ contents studied here are caused by this effect. Consistent with the absence of inclusions in most natural garnets studied, λ-dependent scattering plays no role in their UV absorption. In contrast, in synthetic almandine and spessartine crystals, a different intensity of UV absorption was observed in inclusion-free rims and inclusion-enriched cores. Some of the latter demonstrate typical scattering patterns when measured at crossed polarizers. Received: 10 April 2001 / Accepted: 27 September 2001  相似文献   

14.
The influence on the structure of Fe2+ Mg substitution was studied in synthetic single crystals belonging to the MgCr2O4–FeCr2O4 series produced by flux growth at 900–1200 °C in controlled atmosphere. Samples were analyzed by single-crystal X-ray diffraction, electron microprobe analyses, optical absorption-, infrared- and Mössbauer spectroscopy. The Mössbauer data show that iron occurs almost exclusively as IVFe2+. Only minor Fe3+ (<0.005 apfu) was observed in samples with very low total Fe. Optical absorption spectra show that chromium with few exceptions is present as a trivalent cation at the octahedral site. Additional absorption bands attributable to Cr2+ and Cr3+ at the tetrahedral site are evident in spectra of end-member magnesiochromite and solid-solution crystals with low ferrous contents. Structural parameters a0, u and T–O increase with chromite content, while the M–O bond distance remains nearly constant, with an average value equal to 1.995(1) Å corresponding to the Cr3+ octahedral bond distance. The ideal trend between cell parameter, T–O bond length and Fe2+ content (apfu) is described by the following linear relations: a0=8.3325(5) + 0.0443(8)Fe2+ (Å) and T–O=1.9645(6) + 0.033(1)Fe2+ (Å) Consequently, Fe2+ and Mg tetrahedral bond lengths are equal to 1.998(1) Å and 1.965(1) Å, respectively.  相似文献   

15.
The phase diagram of the NiO-Ga2O3- SiO2 system has been investigated at high temperatures (up to 1550° C) and 1 atm. pressure. The only ternary phases observed in this system are the spinelloid phases I, II, and V, forming on the NiGa2O4-Ni2SiO4 pseudo-binary join at temperatures above 1400° C. Our results show that phase V is stable at higher temperature than phase I, while phase II may be metastable. The stability of phases I and V has been confirmed by the successful growth of single crystals from a silica-rich flux. Phases I, II, and V have been characterized by powder X-ray diffraction and transmission electron microscopy. The dimensions of their orthorhombic unit-cells are: (I) a= 5.7741(5), b=11.712(1), c=8.2387(9) Å; (II) a= 5.765(1), b= 17.619(3), c= 8.238(2) Å; (V) a= 5.7914(4), b=8.7809(7), c=8.2346(6) Å. High resolution electron microscopy has also revealed the formation of microscopic intergrowths similar to those previously observed for the spinelloid phases of the NiO-Al2O3-SiO2 system.  相似文献   

16.
Summary The crystal structure of Ca5(PO4)2SiO4 (silico-carnotite) has been determined from 3358 x-ray diffraction data collected by a counter method and has been refined toR w =0.038,R=0.045, in space group Pnma. The unit cell parameters area=6.737 (1) Å,b=15.508 (2) Å andc=10.132 (1) Å at 24°C;Z=4. The observed density is 3.06 and the calculated density is 3.03 g · cm–3. The crystal contains about 2.5% V2O5 as an impurity. The bond lengths within the tetrahedral anions suggest that substitution or disorder of PO4 3–, SiO4 4– and possibly VO4 3– occurs among the anion sites. The structure has some relationship to that of Ca5(PO4)3OH, the predominant inorganic phase in the human body, but suggests that the Ca5(PO4)3OH type structure may not be stable without some of the OH positions being filled. Ca5(PO4)2SiO4 is more closely related to K3Na(SO4)2 (glaserite) if it is considered that there are systematic cation vacancies in Ca5(PO4)2SiO4.This type of structure is consistent with the view that cation vacancies in the glaserite-type structure account for solid solutions between Ca2SiO4 and Ca3(PO4)2 and between Ca3(PO4)2 and CaNaPO4.
Die Kristallstruktur vonCa 5(PO 4)2 SiO 4 (Silicocarnotit)
Zusammenfassung Die Kristallstruktur von Ca5(PO4)2SiO4 (Silicocarnotit) wurde aus 3358 Röntgendiffraktometer-Daten bestimmt und in Raumgruppe Pnma aufR w =0,038,R=0,045 verfeinert. Die Gitterkonstanten (bei 24° C) sind:a=6,737 (1) Å,b=15,508 (2) Å undc=10,132 (1) Å,Z=4; Dobs.=3,06 g · cm–3, Dexp.=3,03 g · cm–3. Der Kristall enthält etwa 2,5% V2O5 als Verunreinigung. Die Bindungslängen in den tetraedrischen Anionen legen nahe, daß unter den Anionenplätzen gegenseitige Vertretung oder Unordnung von PO4 3–, SiO4 4– und möglicherweise VO4 3– auftritt. Die Struktur zeigt einige Verwandtschaft zu der von Ca5(PO4)3OH, der wichtigsten anorganischen Substanz im menschlichen Körper, weist aber darauf hin, daß eine Struktur vom Ca5(PO4)3OH-Typ ohne Besetzung eines Teiles der OH-Position nicht stabil ist. Ca5(PO4)2SiO4 zeigt engere Beziehungen zu K3Na(SO4)2 (Glaserit), wenn man berücksichtigt, daß in Ca5(PO4)3SiO4 systematische Kationen-Leerstellen sind. Dieser Strukturtyp ist mit derAuffassung in Übereinstimmung, daß Kationenleerstellen für die festen Lösungen zwischen Ca2SiO4 und Ca3(PO4)2 und zwischen Ca3(PO4)2 und CaNaPO4 verantwortlich sind.

With 9 Figures  相似文献   

17.
Metamorphic and magmatic garnets are known to fractionate REE, with generally HREE-enriched patterns, and high Lu/Hf and Sm/Nd ratios, making them very useful as geochemical tracers and in geochronological studies. However, these garnets are typically Al-rich (pyrope, almandine, spessartine, and grossular) and little is known about garnets with a more andraditic (Fe3+) composition, as frequently found in skarn systems. This paper presents LA-ICP-MS data for garnets from the Crown Jewel Au-skarn deposit (USA), discusses the factors controlling incorporation of REE into garnets, and strengthens the potential of garnet REE geochemistry as a tool to help understand the evolution of metasomatic fluids.Garnets from the Crown Jewel deposit range from Adr30Grs70 to almost pure andradite (Adr>99). Fe-rich garnets (Adr>90) are isotropic, whereas Al-rich garnets deviate from cubic symmetry and are anisotropic, often showing sectorial dodecahedral twinning. All garnets are extremely LILE-depleted, Ta, Hf, and Th and reveal a positive correlation of ΣREE3+ with Al content. The Al-rich garnets are relatively enriched in Y, Zr, and Sc and show “typical” HREE-enriched and LREE-depleted patterns with small Eu anomalies. Fe-rich garnets (Adr>90) have much lower ΣREE and exhibit LREE-enriched and HREE-depleted patterns, with a strong positive Eu anomaly. Incorporation of REE into garnet is in part controlled by its crystal chemistry, with REE3+ following a coupled, YAG-type substitution mechanism , whereas Eu2+ substitutes for X2+ cations. Thermodynamic data (e.g., Hmixing) in grossular-andradite mixtures suggest preferential incorporation of HREE in grossular and LREE in more andraditic compositions.Variations in textural and optical features and in garnet geochemistry are largely controlled by external factors, such as fluid composition, W/R ratios, mineral growth kinetics, and metasomatism dynamics, suggesting an overall system that shifts dynamically between internally and externally buffered fluid chemistry driven by fracturing. Al-rich garnets formed by diffusive metasomatism, at low W/R ratios, from host-rock buffered metasomatic fluids. Fe-rich garnets grow rapidly by advective metasomatism, at higher W/R ratios, from magmatic-derived fluids, consistent with an increase in porosity by fracturing.  相似文献   

18.
Summary ?Post-magmatic garnets occur in volcanic breccias at the base of the Neapolitan Yellow Tuff (NYT) formation in the north-western area of the Phlegraean Fields. We report the results of a comprehensive study of these grandites. Garnet is found on the surfaces of tuffaceous blocks or inside their micropores, and is associated with sodalite, sanidine, marialite and amorphous silica. Garnet samples were examined by scanning electron microscopy (SEM), electron probe microanalysis (EPMA), powder and single-crystal X-ray diffraction (XRD) and infrared spectroscopy (IR). SEM observations on morphology showed typical dodecahedral and icositetrahedral habits. EPM analysis showed that they are close to grossular or andradite end members, with only moderate solid solution between them. X-ray study of single crystals showed cubic cell dimensions ao of 11.86 ? (grossular) and 12.04 ? (andradite). IR spectroscopy confirmed the presence of hydroxyls in coexisting garnet and sanidine, 0.06 wt% H2O (garnet) and 0.05–0.07 wt% H2O (sanidine), respectively. Well-crystallized sanidine of an earlier generation showed significantly higher water contents, in the range 0.13–0.23 wt% H2O. Type of occurrence and mineralogical features suggest a post-magmatic (pneumatolitic) genesis for these garnets. This is consistent with the physico-chemical processes linked to the eruptive dynamics of the breccias. Experimental studies of garnet synthesis at 550 °C and 2 kbar provide further support for this concept. Received January 16, 2002; accepted March 18, 2002  相似文献   

19.
Zusammenfassung 1Tc-Strontiohilgardit (Ca, Sr)2 [B5O8(OH)2,Cl] mit Ca : Sr etwa 1 : 1 ist ein neues Mineral der Hilgarditgruppe. Fundpunkt: Reyersbausen (9° 59,7 E, 51° 36,6 N), Grube Königshall-Hindenburg, Flöz Staßfurt in sylvinitischer Ausbildung.Konstanten : triklin-pedial,a 0=6,38 Å,b 0=6,480 Å,c 0=6,608 Å, =75,4°,=61,2°, =60,5°; tafelige-gestreckte Links- und Re chtskristalle, farblos, wasserunlöslich, piezoelektrisch. Härte 5–7, Dichte 2,99 g cm–3;n =1,638,n =1,639,n =1,670; 2V =19°.Neue Daten für die Hilgarditgruppe : 2 M (Cc)-Calciumhilgardit (=Hilgardit) =4 Ca2[B5O3(OH)2Cl], Raumgruppe Cc.3Tc-Calciumhilgardit (=Parahilgardit) = 3 Ca2[B5O3(OH)2Cl]; trinklin-pedial, 0=6,31 Å,b =6,484 Å,c 0=17,50 Å; =84,0°,=79,6°, =60,9°.Die Polymorphiebeziehungen sind geometrisch deutbar durch eine spezielle Art der Polytropie (Stapelung von Links- und Rechtskristallen im Elementarbereich).  相似文献   

20.
Phase relations for the bulk compositions of the celadonites between the MgAl, MgFe3+ and Fe2+Fe3+ types (celadonite = KR2+R3+ Si4O10 (OH)2) under magnetite-iron and nickel-nickel oxide solid-fluid buffers indicate the extent of solid solution possible in this potassic mica series at temperatures between 300° and 430° C at 2 Kb total pressure. Other possible combinations of Mg, Al, Fe ions in octahedrally coordinated sites did not produce single-phase mica products. The ferrous celadonite micas are stable only under oxygen fugacities where magnetite is the stable oxide—where both Fe2+ and Fe3+ can coexist. However the celadonite with the highest thermal stability at 2 Kb total pressure, nickel-nickel oxide buffer conditions is the KMgFe3+Si4O10(OH)2 phase which is stable up to 420°C, well into low grade metamorphic conditions. It is thus apparent that the presence of celadonite or glauconite mica will not be indicative of changing diagenetic conditions.  相似文献   

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